Mono azo dyes



.UNITED- STAT S PATENT OFFICE.

'ALTEB DUISBERG, WINFRIED HENTRIGH, AND LUDWIG ZEH, OI WIESDORF-ON- THE-.RHINE GERMANY, ASSIGNOBS TO GRASSELLI DYESTUI'F COBPQRATION, OF

NEW YORK, 11'. Y.

MONO AZO DYEs Ho Drawing. Application filed l lovember 26, 1924, Serial No. 752,458, and in Germany December 5, 1923.

We have found new and useful improvements in mono azo dyes.

This invention relates to the production of new mono azo d es which are particularly valuable for yeing organic cellulose esters and cellulose ethers suchas cellulose acetate, cellulose formate, ethyl-cellulose, g I methyl-cel1ulose, cellulose actetate fibres,

we have found that the products obtained by combining 'diazotized 'nitro-aniline sulfo or carboxylic acids with aromatic amines having no sulfo groups inthe molemile, or similar amines substituted in the amino group, dye readily such organo-oxycellulose compounds, shades ranging from orange-red to violet and blue being obtained. As first component we can use products such as 2.6-dinitroaniline-4-sulfonic acid, 2.4-dinitroaniline-6-sulfonic acid, 2.4-dinitroaniline-6-carboxylic acid. etc. As coupling compound we use aniline, tolmdine, xylidine, alpha-naphthylam ne, beta-naphthylamine, monomethylamline, di-methylaniline, methyl-aplha-naphthylamine, ethylalpha-naphthylamine, ethyl-beta-naphthylamine, etc.

In order to illustrate further our invention, the following examples are given, the parts being by weight, but it IS understood that the invention is not limited thereto:

Example 1.280 parts of 2.6-dinitroani -line-4-sulfonate of ammonium are diazotized and coupled in mineral acid solution with .143 parts beta-naphthylamine. The dvestufi is isolated in the usual way; it dyes cellulose acetate silk deep red shades. It is in form of its sodium salt a dark brownish powder soluble in water with a reddish color and yielding by reduction with zinc and hydrochloric 'acid 1.2.6-triaminobenzene-4- sullonic acid and amino-beta-naphthylamine.

The dyestufi has inthe form of its am-' monium salt most probably the formula:

I NO] somn. .Ezvample 2.-280 parts of 2.6-dinitroanil ne-t-sulfonate of ammonium are (liazotlzed and coupled in mineral acid solution with 143 parts of alpha-naphthylamin e.

The dyestufl is isolated in the usual way;

it dyes cellulose acetate bordeaux shades.

It is form of its sodium salt a dark browmsh powder soluble in water with a bluish-red color and yielding by reduction with zinc and hydrochloric acid 1.2.6-triaminobenzenei-sulfonic acid and aminoalpha-naphthylamine.

. The dyestufi in the form of its ammonium salt has most probably the formula:

Example 3.280 parts of -2.6-dinitroaniline-4-sulfonate ofammonium are diazotized and coupled in mineral acid solution with 171 parts of etliyl-alpha-naphthylamine. The dyestufi is isolated in the usual way. Violet shades are obtained when cellulose acetate fibres are dyed with this product. It is in form of its sodium salt a dark powder soluble in water with a violetblue color and yielding by reduction with zinc and hydrochloric acid 1.2.6-triaminobenzenelz-sulfonic acid and amino-ethylalpha-naphthylamine.

The dyestufl in the form ofits ammonium salt has probably the formula:

NO; OzNHa potassium Example 5-244 arts of 2.4-dinitroani line-6-carboxylate o ammonium are diazotized and coupled in mineral acid solution with 171 parts of ethyl-beta-naphthylamine. The dyestutf is isolated in the usual way; it dyes cellulose acetate silk in bluish violet shades. It is in form of its sodium salt a dark powder soluble in water with a bluish-violet color and yielding by reduction with zinc and hydrochloric acid 1.2.4

triamino-G-benzoic acid naphthylamine.

The dyestufi in the form of its ammonium salt has probably the formula:

COONH4 and amino-beta- NO No;

We claim 1. The process comprising diazotizing acid substituted dinitroanilines and coupling the diazo compounds obtainedwith aromatic amines havmg no acid'group in the molecule.

2. The process comprising diazotizing dinitroaniline-sulfonic acids and coupling the diazo-compounds obtained with aromatic amines having no acid group in the molecule.

3. The process comprising diazotizing dinitroanilme-sulfonic acids and coupling the diazo compounds obtained with naphl5 thylamines having no acid group in the molecule.

4. The rocess comprising diazotizing dinitroanihne-sulfonic acids and coupling the diazo compounds obtained with naphthylamines having no metal salt-forming group in the molecule.

5. The process comprising diazotizing dinitroaniline-sulfonic acids and coupling the diazo compounds obtained with ethylbeta-naphthylamine.

6. As new products the mono azo dyestuffs which can be obtained by coupling diazotized acid substituted dinitroanilines with aromatic amines having no acid group in the molecules which dyestuffs are reddish to dark brown powders soluble in water with from orange to blue color, dyeing organo-oxy-cellulose compounds from red to 'violet and blue shades and which by reduction with 'zinc and hydrochloric acid yield an acid substituted triaminobenzene and an aromatic'diamine.

7. As new products the mono azo dyestuffs which can be obtained byv coupling diazotized acid substituted dinitroanilines with naphthylamines having no acid group in the molecule, which dyestuifs are red-t0 dark brown powders soluble in water from red to violet to blue shades, dyein organooxy-ccllulose compounds from re to blue shades and which by reduction with zinc and hydrochloric acid yield an acid substituted triaminobenzene and a naphthylenediamine. r

8. As a new product the mono azo dyestuif which can be obtained by coupling 1- diazo-2.6 dinitrobenzene--sulfonate of ammonium with ethyl-alpha-naphthylamine, which dyestuff is a dark brownish powder soluble in water with, violet-blue color, dyeing cellulose acetate violet shades and yielding by reduction with zinc and hydrochloric acid 1.2.6-triaminobenzene-4r-sulfonic acid and amino-ethyl-alpha-naphthylamine.

9. As a new product, an or ano-oxy-cellulose compound material dye with the dyestufi's'of claim 6. 10. As a new product, an organo-oXy-cellulose compound material dyed with the dyestuffs of claim 7 1 11.v As a new product, an organo-oxy-cellulose compound material dyed with the dyestuif of claim 8. i In,testimony whereof we have hereunto set our hands. a

WALTER DUISBERG. WIN'FRIED HENTRICH. LUDWIG ZEH. 

